Selective hydride-mediated conjugate reduction of .alpha.,.beta.-unsaturated carbonyl compounds using [(Ph3P)CuH]6

Mahoney, Wayne S.; Brestensky, Donna M.; Stryker, Jeffrey M.

doi:10.1021/ja00209a048

Cited by 534 publications

(255 citation statements)

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“…Hexa-m-hydrohexakis(triphenylphosphine) hexacopper, also known as Stryker's reagent, is a well-characterized copper(I) hydride reagent for chemoselective conjugate reduction of a,b-unsaturated ketones, [1][2][3][4][5][6][7] esters, 1,4 lactones, 8 nitriles, 9 aldehydes, 3 sulfones, and sulfonates. 6 The reaction is highly chemoselective, and isolated alkenes, halogens, and typical oxygenated functionalities are not reduced under the reaction conditions.…”

Section: Introductionmentioning

confidence: 99%

“…6 The reaction is highly chemoselective, and isolated alkenes, halogens, and typical oxygenated functionalities are not reduced under the reaction conditions. [1][2][3][4][5][6][7] In the presence of several silanes and a catalytic quantity of Stryker's reagent, ketones and aldehydes are reduced to the corresponding alcohols. 10 The conjugated reduction can be performed either stoichiometrically or catalytically in the presence of reducing agents, and the reaction intermediates can be used for further C-C bond formations.…”

Section: Introductionmentioning

confidence: 99%

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Synthetic Applications of Stryker’s Reagent

Fátima¹

2005

Synlett

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Synthetic Applications of Stryker’s Reagent

Fátima¹

2005

Synlett

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“…Hydrogenation of alkyne 6 with PtO 2 under a hydrogen atmosphere, followed by DessMartin oxidation of the resulting saturated alcohol gave ketone 8 in 87% yield over two steps. Although the ketone 8 was alternatively obtained from the Weinreb amide 5 derived from 4 (87%, two steps) via coupling with 3 (49%) and 1,4-reduction of the resulting ynone 7 with Stryker reagent 16 (76%), the former route (77% for three steps from 4) was more practical than the latter one (33% for four steps from 4) both in yield and reagent economy. Removal of the TBS group of 8 with TBAF resulted in the formation of hydroxy ketone 9 in 54% yield as a mixture of its hemiacetal in a 1:1 ratio with 40% recovery of 8 (prolonged reaction time resulted in low yield of 9).…”

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confidence: 99%

Convergent Syntheses of the WXYZ Ring of Maitotoxin and the HIJK Ring of Brevisulcenal-F

et al. 2018

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A convergent method to construct the 6/7/6/6-tetracyclic ether system possessing contiguous angular methyl groups was developed. The key steps of the synthesis involve coupling of a lithium acetylide and an aldehyde, cyclodehydration of a hydroxy ketone to form a dihydropyran, ring expansion of a six-membered ring ketone into a seven-membered one, and methylation of a mixed-thioacetal. Based on this strategy, syntheses of the WXYZ ring of maitotoxin and the HIJK ring of brevisulcenal-F were achieved, and the stereochemistry of the HIJK ring of brevisulcenal-F was confirmed.

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“…After careful optimization, it was found that addition of 4 to the boron enolate of 3 (cHex 2 BCl/Et 3 N) provided the aldol adduct 38 cleanly as a single isomer (70 %), attributable to 1,5-anti stereoinduction [16] from the b-methoxy group in 3 as well as 1,4-syn induction. [27] Finally, dehydration of this b-hydroxy ketone with the Burgess reagent [28] (88 %), followed by 1,4-reduction [29] of the intermediate E enone with [{Ph 3 PCuH} 6 ] gave reidispongiolide A (1) in 75 % yield. All spectroscopic data ( 1 H and 13 C NMR, IR, MS) for the synthetic material were in excellent agreement with that reported [1,30] for natural reidispongiolide A, and correlated with an authentic sample, including HPLC comparison.…”

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confidence: 99%

Total Synthesis of (−)‐Reidispongiolide A, an Actin‐Targeting Marine Macrolide

Paterson¹,

Ashton²,

Britton³

et al. 2007

Angew Chem Int Ed

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Reidispongiolide A (1), isolated by D Auria et al. from the sponge Reidispongia coerulea, which was collected off the coast of New Caledonia, [1] and sphinxolide B (2) [2] are representative members of a structurally unique family of cytotoxic marine macrolides.[3] Their interaction with actin in the cell cytoskeleton leads to microfilament destabilization, and they show potent antiproliferative activity (for example, IC 50 = 0.04 and 0.01 mg mL À1 against human colon carcinoma HT29) and the ability to circumvent multidrug resistance. This profile makes these macrolides valuable molecular probes in cell biology and promising lead compounds for the development of novel chemotherapeutic agents that target actin. [4,5] Their structures comprise a highly oxygenated 26-membered macrolactone, containing a d-lactone ring, and appended with an elaborate side chain at C25 which terminates in an N-vinylformamide group. Through the combination of degradation fragment [2d, 6, 7] synthesis and detailed NMR analysis, we determined the stereochemistry of the entire reidispongiolide macrolide to be that shown in 1 (Scheme 1).[8] Subsequently, Rayment and co-workers [9] reported the X-ray crystal structure of actin-bound reidispongiolide A, assigning the complete configuration and revealing its intriguing mechanism of microfilament destabilization. The sparse natural supply of the reidispongiolides [1] and sphinxolides [2] makes total synthesis of paramount importance, not only to support further biological applications but also to enable structure-activity relationship (SAR) studies. Herein, we report the first total synthesis of reidispongiolide A based on a highly convergent modular assembly process that evolved from our stereochemical analysis groundwork. [7a, 8] As outlined in Scheme 1, our synthetic strategy for reidispongiolide A involves a late-stage introduction of the C30-C36 side-chain segment 3, which incorporates the sensitive N-vinylformamide functionality, through a suitable aldol coupling with the macrolactone aldehyde 4. We elected to disassemble the macrolide 4 into key subunits 5 (C14-C29) and 6 (C4-C13) based on an envisaged second aldol coupling to introduce the stereocenter at C13. The remaining subunit 7 Scheme 1. Synthetic strategy for reidispongiolide A (1) that involves the key building blocks 3, 5, and 6.

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Selective hydride-mediated conjugate reduction of .alpha.,.beta.-unsaturated carbonyl compounds using [(Ph3P)CuH]6

Cited by 534 publications

References 0 publications

Synthetic Applications of Stryker’s Reagent

Synthetic Applications of Stryker’s Reagent

Convergent Syntheses of the WXYZ Ring of Maitotoxin and the HIJK Ring of Brevisulcenal-F

Total Synthesis of (−)‐Reidispongiolide A, an Actin‐Targeting Marine Macrolide

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